CN104937031A - Heat resistant, flame retardant polylactic acid compounds - Google Patents
Heat resistant, flame retardant polylactic acid compounds Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
Significant disadvantages of the use of polylactic acid (PLA), lack of good heat stability and flame retardance, have been overcome by the use of an aryl phosphate in combination with talc. The compound achieves a threshold of 65 DEG C in heat deflection temperature and V-0 flame retardance at 1.6 mm thickness.
Description
Priority request
This application claims the U.S. Provisional Patent Application sequence the 61/753rd submitted on January 16th, 2013, the right of priority of No. 280 (agency's file numbers 12013001), it is by reference to being incorporated into this.
Invention field
The present invention relates to the formulation of the novelty comprising poly(lactic acid), the thermotolerance that this formulation has a raising is to improve this formulation structural integrity in use and flame retardant resistance.
Background technology
Plastics have replaced glass, metal and timber-work because plastics can carry out engineering design and can not broken, get rusty or rot.The weather resistance of plastics also causes disposal difficulties.And many Plastic Resins are obtained by petroleum chemicals, and petroleum chemicals have the problem of long run supply and cost aspect.
Therefore, people are striving to find biologically-derived continuable thermoplastic resin resource, preferably can degrade or compost thus solve those thermoplastic resin resources of disposal difficulties.
Developed poly(lactic acid) (also referred to as polylactide or PLA) as the thermoplastic resin from the sustainable source of biology, it can replace the resin being derived from petroleum chemicals.
PLA also needs to benefit from interpolation fire retardant, particularly non-halogenated flame retardent.
Summary of the invention
Although poly(lactic acid) may be the one in the three kinds of modal biologically-derived resins be just developed, compared with the fossil resins derived therefrom replaced with its intention, poly(lactic acid) has unique shortcoming, and namely it has poor heat deflection temperature (HDT).
According to ASTM D648 agreement, heat deflection temperature (HDT) (HDT) is measuring of the flexure of sample under deflection load.Deflection load can be any one in two groups of settings.In the present invention, 66 pounds/square inch (psi) or 455 kPas (kPa) are used to carry out comparing and measuring of thermal flexibility.
The problem of poly(lactic acid) is that its heat deflection temperature (HDT) under the flexible payload of 455kPa is about 55 DEG C or 131 °F.In other words, at Arizona State automotive interior in the daytime in summer, PLA is firm not, therefore can not as the thermoplastic resin being molded as passenger carriage parts, can not be used as portable electronic device outer case to be placed on seat, or a slice packaging that can not be used as containing perishable foodstuff in grocery bag is placed on the base plate in automobile.
The problem of PLA is that it does not have enough thermotolerances, is not therefore in fact considered as the substitute of the thermoplastic resin that the current fossil used in many ordinary plastic articles derives.
Add fire retardant to PLA formulation and may adversely affect other character, such as heat deflection temperature (HDT).
Needed for this area is heat-resisting, fire-retardant poly(lactic acid) formulation, thus the heat-resisting thermoplasticity formulation that the replaceable wherein thermoplastic resin of such formulation is made up of petrochemical industry source (being obtained by mining in the earth or drilling well), acceptable non-halogenated fire retardant character is also provided simultaneously.
In some terminal applies, another problem of PLA is that its toughness (namely shock-resistant) is not enough.Even if having thermotolerance, fragility thermoplasticity formulation is also unsuitable for commercial applications.
The present invention solves this problem by following manner: using the talcum of PLA and certain content, as the aryl phosphate of non-halogenated flame retardent and optional anti-impact modifier compounding, thus described PLA formulation has enough thermotolerances, flame retardant resistance and impelling strength replaces conventional thermoplasticity formulation to allow described PLA formulation.
This area all needs to solve above-mentioned temperature resistance problem for a long time.The natural work company (NatureWorks, LLC) of principal manufacturer of PLA is in website
www.natureworksllc.comreported the acrylonitrile-butadiene-styrene (ABS) (ABS) by adding the most nearly 50 % by weight in PLA in disclosed document, generate 50-50PLA-ABS blend, its HDT only improves 2 DEG C than the HDT of pure PLA fluoropolymer resin.The ABS reaching most 80 % by weight is added to PLA causes HDT to improve 30 DEG C really, but in the mixture, more as the abs polymer using PLA modification.
And, this area all needs to solve this temperature resistance problem for a long time, universals in some industry are HDT that PLA formulation preferably should have at least 65 DEG C under 66psi, so as to become from the sustainable source of biology can the thermoplasticity formulation of practical application in industry.
This area needs a kind of method to improve the actual HDT value of PLA, can keep again gained formulation basically in fact or PLA formulation simultaneously.
In the present invention, PLA should remain " main ingredient ", means that the amount shared by PLA is in formulation is at least about 30 % by weight (30%).
Surprisingly, the talcum of PLA and 1-8 % by weight, aryl phosphate and optional acrylic impact modifier are combined, the HDT of PLA formulation can be increased to higher than 65 DEG C.
One aspect of the present invention is heat-resisting, fire-retardant poly(lactic acid) formulation, and it comprises: (a) poly(lactic acid); (b) polycarbonate; C () content is the talcum of the about 1-8 % by weight of formulation; (d) aryl phosphate.
Another aspect of the present invention to be shaped the flame retardant plastics goods obtained by the formulation described in the paragraph be close to above.
The embodiment of existing for associative list unexpected technique effect and embodiment are explained further the feature and advantage of formulation of the present invention.
The specific embodiment of the present invention
PLA
PLA is well-known biological polymer, has the monomer recurring group shown in following general formula I:
PLA can be poly-D-rac-Lactide, PLLA, or their combination.PLA can be purchased from the natural work company (NatureWorks, LLC) being positioned at whole world fabrication region.The PLA of any grade can be used for the present invention.At present, preferably class 4 042D and 4032D.The number-average molecular weight of PLA can be any numerical value that is obtainable or that will put goods on the market in future in industrial rank at present.To be manufactured benefiting from by PLA with regard to the intended application of current plastics and formulation of the present invention thermotolerance with regard to, suitable PLA should be the starting point building formulation of the present invention.
polycarbonate
PC is really main force's polymkeric substance that polymerization scholar those of ordinary skill in the art know.Its chemical feature can be aliphatics or aromatic series.It can be homopolymer or multipolymer.
Any commercially available PC is candidate materials used in the present invention.
Commercially available PC has multiple grade can purchased from many commercial manufacturers of any amount, comprise Sepik Innovative Plastics (SABIC Innovative Plastics) (GE plastics (General ElectricPlastics) in the past), Dow Chemical (Dow Chemical), Beyer Co., Ltd (Bayer) and mondial other companies many.
At 300 DEG C, measure under 1.2 kilogram force loads about 2.5 grams/10 minutes to about 60 grams/10 minutes that measure under load at 250 DEG C, 1.2 kilograms according to ASTM D-1238 for the melt flow index (MFR) of PC of the present invention.
talcum heat-resistant agent
The well-known functional stuffing for compounding of polymers thing of talcum.The surprisingly talcum of the certain content non-halogenated flame retardent that makes aryl phosphate can be used as in PLA/PC blend.Specifically, as described in the following examples, in order to obtain higher than the V-0 flame retardant resistance (ASTM D-635) under HDT and the 1.6mm thickness of 65 DEG C, the content of talcum can be about 1 % by weight-8 % by weight of formulation.
Talcum is naturally occurring mineral, is totally defined as hydrous magnesium silicate, and its chemical index service numbering is CAS#14807-96-6.Its chemical formula is 3MgO4SiO
2h
2o.
Talcum can be bought from multiple commercial source.The non-limitative example of this talcum used in the present invention is Jetfil
tMboard talcum (purchased from American Lu Zenaka company (Luzenac America), Flextalc
tMboard talcum (purchased from specialty minerals company (Specialty Minerals)), Talcron
tMboard talcum is (purchased from mineral technologies company (Mineral Technologies) and Mistron
tMboard talcum (purchased from American Lu Zenaka company).
The granularity of talcum can be about 0.5 μm of-Yue 20 μm, and preferably about 0.7 μm of-Yue 7 μm.
fire retardant
Halogen-free flame retardants for thermoplasticity formulation can be selected from multiple phosphorous chemical substance.In the present invention, aryl phosphate is used as non-halogenated flame retardent.A kind of aryl phosphate is Resorcinol two (diphenyl phoshate), and its chemical index service numbering is CAS#57583-54-7.A kind of commercial source of Resorcinol two (diphenyl phoshate) is REOFOS
tMboard fire retardant (purchased from Chi Mute company (Chemtura)).Another kind of aryl phosphate is commercially available Fyrolflex
tMsol-DP (the ICL Industrial products company (ICLIndustrialProducts) purchased from St. Louis, Missouri).Consider that CAS numbering is secret of the trade, ICL Industrial products company does not publish the concrete chemical information of this aryl phosphate, but really disclosing this aryl phosphate is oligomeric, free-pouring solid phosphate ester fire retardant, its phosphorus content is 10.7%, proportion is 1.3, fusion range is 101-108 DEG C, and triphenyl content is less than about 1%.When carrying out thermogravimetric analysis (10 DEG C/min, air), the loss of aryl phosphate is as follows: at 300 DEG C 2%; At 335 DEG C 5%; With 350 DEG C at 10%.
optional impact modifier
Any conventional impact modified dose all candidate can be used for formulation of the present invention.Core/shell impact modifier, rubber-like impact modifier etc. is suitable.
In various impact modifier alternative option, Paraloid
tMboard core/shell acrylic impact modifier (purchased from Dow Chemical (DowChemical)) is suitable.Siloxanes (silicone)-acrylic rubber impact modifiers such as MetablenS-2030 (is also suitable purchased from mitsubishi rayon (MitsubishiRayon).
In the present invention, acrylic impact modifier is optional still preferred, because it is more than not needing the application of these character to need the application of impact-resistance or toughness.
optional tear drop inhibitor
Any conventional tear drop inhibitor is all for candidate material of the present invention, because tear drop inhibitor helps described formulation to keep integrity when burning.
Pointed by the open source literature of Ka Naka (Kaneka) company, the formulation containing polycarbonate of siloxanes/(methyl) acrylate core/shell impact modifier is used to be benefited as tetrafluoroethylene (PTFE) by adding tear drop inhibitor.Formulation of the present invention preferably comprises a small amount of PTFE.
Use another added advantage of PTFE be known it be a kind of lubricant, the processing of described formulation when melt-mixing or described plastics are finally shaped can be helped.
Although PTFE fluoridizes, comprise very micro-this kind of component (if any) in formulation of the present invention and this formulation can not be made not have qualification to regard non-halogenated fire retardant formulation as.
other optional additive
Formulation of the present invention can comprise other common plastics additive, and its consumption is enough to make formulation have required working properties or performance characteristics.The amount of additive should not cause waste or to the processing of formulation or detrimental.The technician of thermoplasticity compounding art, only must with reference to some documents without the need to too much experiment, such as from " plastic design storehouse " (PlasticsDesignLibrary) (www.elsevier.com) "
plastics additive data storehouse" (
plasticsAdditivesDatabase) (2004), many dissimilar additives just can be selected to add in formulation of the present invention.
The non-limitative example of optional additive comprises adhesion promotor; Biocide (antiseptic-germicide, mycocide and mould inhibitor), anti-fogging agent; Static inhibitor; Binding agent, pore forming material and whipping agent; Dispersion agent; Fireproofing agent, fire retardant and smog inhibitor; Initiator; Lubricant; Pigment, tinting material and dyestuff; Softening agent; Processing aid; Releasing agent; Surface slip agent and antiblocking agent; Stablizer; Stearate/ester; Ultraviolet absorbers; Viscosity modifier; Wax; With their combination.Such as, black pigment masterbatch can be added, such as Techmaster710021 masterbatch (the Te Ke blend company limited (TechBlendS.E.C.) purchased from Quebec, CAN Li Sailiu (Saint-Jean-surRichelieu)).
Table 1 shows the acceptable, required of each component used in the present invention and preferred scope, is all expressed as the weight percentage (% by weight) accounting for whole formulation.
processing
The preparation of formulation of the present invention is uncomplicated, can interval or operate continuously mode obtain.
The married operation carried out with continuous processing carries out usually in an extruder, and the temperature of this forcing machine is elevated to be enough to polymeric matrix is melted, and can add solids component additive at extrusion machine head or forcing machine downstream.Forcing machine speed can be about 50-700 rev/min (rpm), is preferably about 100-300rpm.Usually, make granular by the product exported from forcing machine, confession is extruded later or mould-forming is polymer product.
The married operation carried out with batch technology carries out usually in a mixer, and the temperature of this mixing tank is also elevated to be enough to polymeric matrix is melted, to add solids component additive.Mixing velocity is 60-1000rpm.In addition, be less size by the product chopping exported from mixing tank, confession is extruded later or mould-forming is polymer product.
Optionally before interval or continuous fusion mixing, can dry each component, thus contribute to reducing in melting mixing container the degraded of moisture-activated or the possibility of reaction occur.Or, can make otherwise to reduce the possibility that degraded occurs, such as, in formula, introduce dehumidizier or siccative, in melting mixing container, apply vacuum, etc.Any one in these technology or their combination all make component dry before melting mixing or in melting mixing process.
Follow-up to extrude or molding technology is that thermoplastic polymer engineering field technician is well-known.Not needing too much experiment, only needing with reference to such as " extruding, authority's processing guide and handbook " (Extrusion, The Definitive Processing Guide and Handbook); " molded parts shrinks and warpage handbook " (Handbook of Molded Part Shrinkage andWarpage); " professional molding technology " (Specialized Molding Techniques); " Rotomolding techniques " (Rotational Molding Technology) and " mould, instrument and die head repairing welding catcher volume " (Handbook of Mold, Tool and Die Repair Welding) reference of (publishing (www.elsevier.com) by plastic design storehouse) and so on, those skilled in the art just can use formulation of the present invention to obtain to have the goods of any conceivable shape and outward appearance.
Do not consider the optional drying in melting mixing process or other technology, have been found that the moisture content minimized after molding in formulation has a direct impact the performance characteristics comprising heat deflection temperature (HDT).Moisture content application is less than about 0.2%.Relative to close about 4 hours, dry amount closer to about 48 hours, should be preferably 4-12 hour, and to realize the blended formulation of substantially dry after molding, namely moisture content is less than 0.2%.In order to be reduced in the possibility close to the heat deflection temperature (HDT) drying of 65 DEG C, when not adopting vacuum, temperature can be up to about 60 DEG C.In fact, do not need too much experiment, those of ordinary skill in the art can determine best time, temperature and atmospheric combination, to shorten time of drying, farthest increase dry amount again simultaneously, and do not need the temperature of the performance close to the formulation that will degraded or impact caused to be shaped as molding or extruded product.
Practicality of the present invention
Any plastics all can select the application for formulation of the present invention.Because achieved now the heat durability of PLA, all types of plastics of HDT that the needs prepared of the polymkeric substance before derived by fossil the raise HDT of at least 65 DEG C (preferably under 66psi), can be prepared by continuable PLA compounding of polymers thing now.
The plastics prepared by formulation of the present invention by molding or extrusion molding, for transport, household electrical appliance, electronics, building and construction, biomedicine, packaging and consumer market.
The non-limitative example benefiting from the final plastics of non-halogenated fire retardant PLA/PC formulation comprises all types of electronic products part, such as computer server shell, phone cover, camera etc.
Following examples prove unexpected feature of the present invention.
Embodiment
comparative examples A and embodiment 1-9
Table 2 shows extrusion condition.Table 3 shows molding (molding) condition.Table 4 show formula and the proportion according to ASTM D-792, the tensile property according to ASTM D-638, the flexible nature according to ASTM D-790, notched izod (NotchedIzod) shock strength according to ASTM D-256, according to the HDT of ASTM D648 under 66psi and the flame retardant resistance according to ASTM D-635.
Table 4 describes and produces experimentation of the present invention.Embodiment 1-5 all proves that the Resorcinol two (diphenyl phoshate) of the talcum and 15 weight percentage combining 1-8 weight percentage prepares PLA/PC thermoplasticity formulation, and its HDT is at least 65 DEG C and flame test grade under 3.2 millimeters and 1.6 mm of thickness is V-0.
Comparative examples A shows, the Resorcinol two (diphenyl phoshate) containing 15 % by weight but without even can not obtain during talcum V-1 flame retardant resistance grading.Under all thickness, V-2 flame retardant resistance is completely unacceptable.
Embodiment 4 and 6-8 show constantly to be that the Resorcinol two (diphenyl phoshate) of the difference amount of PLA and 10-15 % by weight of the talcum of 2 % by weight and the difference amount of 30-40 % by weight obtains the HDT of at least 65 DEG C and the flame test under 3.2 millimeters and 1.6 mm of thickness is V-0.This means, without the need to undo experimentation, the amount that those of ordinary skill in the art can change composition prepares various acceptable heat-resisting, the fire-retardant PLA/PC thermoplasticity formulation that wherein PLA is main ingredient.
Embodiment 3 and 4 shows to realize V-0 flame retardation under 0.8 mm of thickness and the HDT higher than 69 DEG C.
In various embodiments, embodiment 8 and 9 is at present preferred, because they all have V-0 under 3.2 and 1.6 mm of thickness and the HDT higher than 75 DEG C.
embodiment 10-12
Prepared 3 kinds of other preparations according to the extrusion condition of table 2, and the condition of moulding of use table 3 is molded as test sample subsequently.
Table 5 show formula and the proportion according to ASTM D-792, the tensile property according to ASTM D-638, the flexible nature according to ASTM D-790, notched izod (NotchedIzod) shock strength according to ASTM D-256, according to the HDT of ASTM D648 under 66psi, according to the flame retardant resistance of ASTMD-635 and the mold shrinkage according to ASTM D-955.
Embodiment 10-12 shows to use REOFOS
tMresorcinol two (diphenyl phoshate) or Fyrolflex
tMsol-DP phosphoric acid ester, as aryl phosphate, can provide excellent flame-retardant nature.
Embodiment 12 shows, compared with embodiment 11, silicone-acrylic base impact modifier can improve the toughness of Resorcinol two (diphenyl phoshate), as passed through measured by breach Ai Zuode (NotchedIzod).
The invention is not restricted to above-mentioned embodiment.It is below appended claims.
Claims (15)
1. heat-resisting, a fire-retardant poly(lactic acid) formulation, it comprises:
(a) poly(lactic acid);
(b) polycarbonate;
C () accounts for the talcum of about 1 % by weight-Yue 8 % by weight amount of described formulation; With
(d) aryl phosphate.
2. formulation as claimed in claim 1, it is characterized in that, described aryl phosphate is selected from lower group:
(a) Resorcinol two (diphenyl phoshate) and
(b) oligomeric, free-flowing solid aryl phosphate ester fire retardant, its phosphorus content is 10.7%, proportion is 1.3, fusion range is 101-108 DEG C and triphenyl content is less than about 1%.
3. as formulation according to claim 1 or claim 2, it is characterized in that, when testing under 1.6 mm of thickness according to ASTM test No. D-635, described formulation has V-0 grading.
4. formulation as claimed in claim 1, it is characterized in that, described aryl phosphate is Resorcinol two (diphenyl phoshate), the talc content of wherein said formulation is the about 2-about 4 % by weight of described formulation, and wherein when testing under 0.8 mm of thickness according to ASTM test No. D-635, described formulation has V-0 grading.
5. formulation as claimed in claim 3, it is characterized in that, when testing under 66PSI according to ASTM D-648, the heat-drawn wire of described formulation is higher than 65 DEG C.
6. formulation as claimed in claim 3, it is characterized in that, the talc content of described formulation is less than about 8 % by weight of described formulation, wherein said formulation comprises Resorcinol two (diphenyl phoshate) as described aryl phosphate and its content is less than about 15 % by weight of described formulation, and wherein when testing under 66PSI according to ASTM D-648, the heat-drawn wire of described formulation is higher than 69 DEG C.
7. formulation as claimed in claim 1, it is characterized in that optionally there is acrylic impact modifier, its content is the about 1-about 15 % by weight of described formulation.
8. the formulation according to any one of claim 1-7, is characterized in that, described poly(lactic acid) comprises poly-D-rac-Lactide, PLLA or both combinations, and wherein poly(lactic acid) is present in described formulation with the amount of about 20 to about 50 % by weight scopes.
9. the formulation according to any one of claim 1-7, is characterized in that, described polycarbonate is present in described formulation with the amount of about 40 to about 60 % by weight.
10. formulation as claimed in claim 7, it is characterized in that, described impact modifier is core/shell acrylic polymers or silicone-acrylic base rubber.
11. formulations according to any one of claim 1-10, it is characterized in that, described formulation also comprises the optional additive being selected from lower group: adhesion promotor; Biocide; Anti-fogging agent; Static inhibitor; Tackiness agent, pore forming material and whipping agent; Dispersion agent; Initiator; Lubricant; Pigment, tinting material and dyestuff; Softening agent; Processing aid; Releasing agent; Surface slip agent and antiblocking agent; Stablizer; Stearate/ester; Ultraviolet absorbers; Viscosity modifier; Wax; And their combination.
12. 1 kinds of formulations according to any one of claim 1-11 are shaped the plastics obtained.
13. goods as claimed in claim 12, it is characterized in that, described goods are moldings or extrude, and wherein said goods form for transport, household electrical appliance, electronics, building and construction, packaging or consumer market.
14. 1 kinds of methods preparing the formulation according to any one of claim 1-12, said method comprising the steps of
A () assembles the composition comprising poly(lactic acid), polycarbonate, talcum and aryl phosphate,
B their melting mixing are become formulation by (), this formulation is used for subsequently being configured as plastics, and described plastics form for transport, household electrical appliance, electronics, building and construction, packaging or consumer market.
15. methods preparing formulation as claimed in claim 14, it is characterized in that, described method is further comprising the steps of:
C described formulation is dried to water content and is less than 0.2% by (); With
D described formulation is configured as plastics by (), described plastics are used for transport, household electrical appliance, electronics, building and construction, packaging or consumer market.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361753280P | 2013-01-16 | 2013-01-16 | |
| US61/753,280 | 2013-01-16 | ||
| PCT/US2014/011648 WO2014113453A1 (en) | 2013-01-16 | 2014-01-15 | Heat resistant, flame retardant polylactic acid compounds |
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| CN104937031A true CN104937031A (en) | 2015-09-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207841A (en) * | 2014-12-23 | 2017-09-26 | 沙特基础工业全球技术公司 | Reinforced polycarbonate compositions |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013028857A1 (en) * | 2011-08-25 | 2013-02-28 | Polyone Corporation | Heat resistant polylactic acid compounds |
| US9534116B2 (en) | 2012-10-17 | 2017-01-03 | Polyone Corporation | Flame retardant polylactic acid compounds |
| US9309403B2 (en) | 2012-10-17 | 2016-04-12 | Polyone Corporation | Heat resistant, flame retardant polylactic acid compounds |
| CA2929129C (en) | 2015-05-07 | 2023-08-01 | University Of Guelph | Durable high performance heat resistant polycarbonate (pc) and polylactide (pla) blends and compositions and methods of making those |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2276335T3 (en) * | 2003-07-18 | 2007-06-16 | Ciba Specialty Chemicals Holding Inc. | FLAME DELAY POLYLACTIC ACID. |
| US7368511B2 (en) * | 2003-12-22 | 2008-05-06 | Eastman Chemical Company | Polymer blends with improved rheology and improved unnotched impact strength |
| JP2005320469A (en) * | 2004-05-11 | 2005-11-17 | Idemitsu Kosan Co Ltd | Polycarbonate resin composition and molded article |
| ATE509985T1 (en) * | 2004-09-17 | 2011-06-15 | Toray Industries | RESIN COMPOSITION AND MOLDED BODY THEREOF |
| JP5424563B2 (en) * | 2006-01-18 | 2014-02-26 | 帝人株式会社 | Method for producing resin composition |
| CN101671476B (en) * | 2008-09-11 | 2013-04-10 | 拜耳材料科技(中国)有限公司 | Blend of aromatic polycarbonate and polylactic acid, preparation method and application thereof |
| KR20100079518A (en) * | 2008-12-31 | 2010-07-08 | 지에스칼텍스 주식회사 | Polymeric composite materials comprising poly lactic acid |
| EP2527400B1 (en) * | 2010-01-18 | 2016-03-30 | Teijin Limited | Polylactic acid composition |
| JP5881285B2 (en) * | 2010-10-27 | 2016-03-09 | 帝人株式会社 | Flame retardant resin composition and molded product therefrom |
| WO2013028857A1 (en) * | 2011-08-25 | 2013-02-28 | Polyone Corporation | Heat resistant polylactic acid compounds |
| US9023922B2 (en) * | 2012-05-24 | 2015-05-05 | Sabic Global Technologies B.V. | Flame retardant compositions, articles comprising the same and methods of manufacture thereof |
-
2013
- 2013-03-12 US US13/797,333 patent/US20140200295A1/en not_active Abandoned
-
2014
- 2014-01-15 WO PCT/US2014/011648 patent/WO2014113453A1/en active Application Filing
- 2014-01-15 CN CN201480004932.1A patent/CN104937031A/en active Pending
-
2016
- 2016-08-26 US US15/249,208 patent/US20160362550A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207841A (en) * | 2014-12-23 | 2017-09-26 | 沙特基础工业全球技术公司 | Reinforced polycarbonate compositions |
| US10240039B2 (en) | 2014-12-23 | 2019-03-26 | Sabic Global Technologies B.V. | Reinforced polycarbonate compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014113453A1 (en) | 2014-07-24 |
| US20160362550A1 (en) | 2016-12-15 |
| US20140200295A1 (en) | 2014-07-17 |
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